Reaction products of a sulfur chloride and n,n&#39;-dialkylphenylenediamines



United States Patent 3,100,765 REACTION PRODUQTS OF A SULFUR CHLORIDE AND N,N-DIALKYLPHENYLENEDIAMINES Harry E. Albert, Lafayette Hill, Pa, assignor to The Firestone Tire & Rubber Company, Akron, Ohio, a

corporation of Ohio No Drawing. Filed Sept. 16, 1959, Ser. No. 840,224

1 Claim. (til. 260-432) This invention relates to the reaction products of the sulfur chlorides and certain N,N'-dialkylphenylenediamines.

Various phenylenediamine derivatives have previously been used in rubber. N,N-diarylphenylenediamines have been used as flex-cracking inhibitors. N,N-dialkylphenylenediamines have been used as antiozonants.

Of the latter, N,N-di-sec.butylap-phenylene'diamine is commercially available [and is a powerful antiozonant. However, it is quite toxic. Also, its volatility causes losses during mixing and curing and contributes to continuing loss during the life of the vulcanized rubber article containing this material.

The sulfides of this invention are more persistent than the phenylenediamines from which they are derived, and they have little or no toxicity. They are powerful antiozonants. There are three different types of rubber stabilizers, viz., antiozxonants, antioxidants, and flex-cracking inhibi' tors. These are not to be confused with one another. Each functions characteristically, and it is considered unusual if any one of these types of stabilizers performs more than the one function.

Crabtree and Kemp in an article in Industrial and Engi neering Chemistry, vol. 38, starting at page 278 (1946), explain the difference in the destructive action of oxygen and ozone on rubber. The light catalyzed oxidation which occurs during outdoor exposure forms a skin and crazed appearance over the exposed surface of the rub bet. Ozone, however, even in very low concentration, induces cracking in rubber, but only if the rubber is stretched (C. H. Leigh-Dugmore, Rubber Age and Synthetics, November and December 1952). The cracks are perpendicular to the direction of stretch. Such cracking can owur in the absence of light. The compounds which inhibit ozone deterioration of rubber are referred to herein as antiozonants.

Tires are stressed when inflated. While a tire is at rest it is stretched statically, and on a moving vehicle it is stretched dynamically, i.e., it undergoes alternating stretching and relaxing. Some of the antiozonants are more effective in static tests and others are more effective in dynamic tests. Antiozonants which are effective under both conditions will be desired [for tires, but for other rubber products an antiozonant which does not meet both tests may be used.

The inhibiting effect of the anticzonants of this invention on rubber was determined by treatment of unaged, cured stocks with air of controlled ozone content in specially designed equipment, and also by outdoor exposure to natural Weathering. The tests were conducted with one-half inch dumbbell samples of approximately 100 gauge thickness. The special apparatus for testing with air of controlled ozone content, and the method of testing therein are described in the articles by Ford and Cooper, appearing in India Rubber World for September and October 1951, entitled A Study of the Factors A;f- [footing the Weathering of Rubber-Like Materials-J and II. The following reports refer to tests in which the ozone concentration was maintained at 60 parts per 100,000,000 under the conditions stated. Two types of tests were conducted. In one type, called the dynamic test, the sample was repeatedly stretched between the limits of 0 and 20 percent elongation at the rate of 108 cycles per minute. In the other type of test, the static test, the samples were stretched at 12.5 percent elongation throughout the test. On completion ct each test the nurnber and size of the cracks in each sample were compared visually with the number and size of the cracks in a control strip and in the blank strip from the same masterbatch which contained no antiozone agent, both of which were cured and tested at the same time as the test sample. The number of craclcs was reported on an arbitrary scale as follows: none, very few, few, moderate, moderate-to-numerous (or mod.-num.), and numerous. The size of the cracks was reported according to an arbitrary scale as follows: very slight, slight, moderate, moderately severe (or mod. sev.), and very severe.

In the first of the reported tests 2.0 parts by weight of an antiozonant were added to the master-batch formula for each parts of rubber present. The results include data on the tensile properties of the cured rubber stocks before and after aging in an oven under the conditions stated. The modulus and tensile strength are given in pounds per square inch, and the elongation is reported as percent of stretch at the break. These data are included (to show that the antiozonants have nosubstantial deleterious effect upon the cure or upon the aging of the cured stocks.

The antiozonants are effective in the vulcanizates of both natural and synthetic diene rubbers, as, for example, those produced .by polymerizing or coplymerizing a conjugated diene, as, for example, 1,3-butadiene (or hydrocarbon homologue thereof) with a vinyl monomer as, for example, styrene, acrylonitrile, methaorylonitrile, or an ester of vinyl alcohol, an ester of acrylic or methvacrylic acid, v-inylpyridine, vinylcarbazole or other lowmolecularaveight vinyl monomer.

The rubber can be vulcanized with sulfur or a sulfur donor, or with a cross-linking agent such as a dithiol, nitroor nitroso-compound, quinone dioxime, etc. Known vulcanization accelerators are useful in speeding up the vulcanization process and are operative herein, especially the relatively active accelerators including the thiazole sultan-amides, e.g., N:cyclohexyl-2-benzothiazolesulfenamide, thiazoline sulfenamides, thiccarbamyl sulfenatnides, mercaptothiazoles, mercaptothiazolines, thiazolyl monoand disulfides, the N,N-disubstituted dithiocarrbamates, the thiurarn sulfides, the xanthogen sulfides, and metallic salts of mercaptothiazoles or mercaptcthiazolines or dithiocarbarnic acids.

One or more accelerator activators are often used with any of the accelerators mentioned, and such activators include the various derivatives of guanidine known in the rubber art, amine salts of inorganic and organic acids, various amines themselves, and alkaline salts such as sodium acetate and the like, as well as other activators known in the art. Additionally, two or more accelerators or accelerator combinations are sometimes desirable in a single rubber compound. Many of the accelerators mentioned above are suitable in latex formulations, especially such common accelerators as piperidinium pentamethylene dithiocarbarnate, zinc butylxanthate, zinc ethylxanthate, zinc salt of mercaptcbenzothiazole, zinc dimethyldithiocarbam ate, and zinc dibutyldithiocarbamate. Although vulcanization is usually accomplished by heating a vulcanizable rubber composition at a temperature in the range of 240 to 400 F. for a time ranging from several hours to a few seconds, vulcanization does take place at lower temperatures such as ordinary room temperature. It is quite common to Mulcanize a latex film containing an ultra-accelerator by allowing the film to remain at room temperature for several hours or a few days.

The lantiozon-ants of this invention are reaction products of sulfur chloride ('S Cl or sulfur dichloride (SCI and an N,N'-dia1kyl-oor p-phenylenediamine-in which the alkyl groups may contain up to 12 carbon atoms. The antiozon ants are, for example, obtainable from the following phcnylenediamines and their equivalents.

- and p-Phenylenediamines The reaction products are obtained by reacting a N,N- dialkylphenylenediamine, as defined, with a sulfur chloride, preferably in the presence of an inert solvent, and neutralizing the liberated hydrogen chloride by substantially simultaneous addition of an alkaline material to [the reaction mixture. They are hydrogen chloride free. The following examples are illustrative.

EXAMPLE 1 Twenty-two g. (0.1 mole) of N,N-di-sec.-butyl-pphenylenediamine was dissolved in 100 ml. n-hexanc.

Seven-g. (0.052 mole) of S Cl was weighed out and about one-third of this was added to the hexane solution. Eleven and nine-tenths grams of K CO in 100 ml. of water were added to neutralize the H01 liberated in the reaction, and then the remainder of the S Cl was added. The reaction product is crude bi-s(N,N'-di-sec.-butyl-pphenylenediiamine) disulfide. A yield of 24.0 g. of a dark liquid was obtained.

EXAMPLE 2 A solution of 111 g. (0.33 mole) of N,N'-di(l-methylheptyl)-p-phenylenediamine in 500 ml. of benzene was placed in a liter 3-1eck flask provided with a motor driven stirrer, a thermometer, and two addition funnels. Sulfur dichloride (l7 g.-=0.165 mole) was added dropwise during stirring while simultaneously a solution of 13.2 g. (0.33 mole) of sodium hydroxide in 300 ml. of Water was also added to neutralize the liberated hydrogen chloride. The addition required 20 minutes during which time the temperature of the reaction mixture rose from 34 to 45 C. The reaction mixture was stirred for 1 hour, then the benzene layer was separated and washed with water. The benzene was removed under reduced pressure leaving a black somewhat viscous product which weighed 95 g. Analysis showed this prodnet to contain 3.22% sulfur.

EXAMPLE 3 A solution of 111 g. (0.33 mole) of N,N'-di(l-metl1ylheptyD-p-phenylenediamine in 500 ml. of benzene was placed in a liter 3-neck fiask'provided with a motor driven stirrer, a thermometer and two addition funnels.

Sulfur dichloride (34 g. =0.33 inole) was added dropwise during stirring While simultaneously a solution of 26.5 g. (0.66 mole) of sodium hydroxide in 300 ml. of water was also added to neutnalize the liberated hydrogen chloride. The addition required 40 minutes during which time interval the temperature of the reaction mixture rose from 23 to 52 C. The reaction mixture was stirred for 2 "hours, then the benzene layer was separated and washed twice with water. The benzene was removed under reduced pressure leaving a somewhat visco us liquid product which weighed 107 g.

EXAMPLE 4 Using a procedure similar to that employed in Example'2 and Example 3, 111 g. (0.33 mole) of N,N- di(l-methylheptyl)-p-phenylenediamine reacted with 68 g. (0.66 mole) of sulfur dichloride using 53 g. (1.32 moles) of sodium hydroxide for neutralization to give 116 g. of a black viscous liquid. This product was found to contain 12.97% sulfur.

EXAMPLE 5 A solution of 55 g. (0.25 mole) of N,N-di-sec.- butyl-p-phenylenediamine in 500 ml. of benzene was placed in a 1-liter 3-neck flask provided with a motor driven stirrer, a thermometer, and two addition funnels. Sulfur dichloride (52 g.=0.5 mole) was added dropwise during stirring. Simultaneously a solution of 40 g. (1 mole) of sodium hydroxide in 300 ml. of water was added to neutralize the liberated hydrogen chloride. The addition required /2 hour, during which time the temperature of the reaction mixture rose from 23 C. to 67 C. After stirring for 1 hour, the benzene layer was separated and washed with water. Removal of the solvent under reduced pressure gave a black somewhat soft solid. The sulfur content of the product was found to be 22.59%.

EXAMPLE 6 EXAMPLE 7 Using the procedure outline in Example 5, 55 g. (0.25

mole) of N,N'-di-sec.-butyl-p-phenylenediamine reacted with 13 g. (0.12 mole) of sulfur dichloride with 10 g.

(0.25 mole) of sodium hydroxide for neutralization to give 54 g. of a black, somewhat viscous product. Analysis showed that this product contained 6.07% sulfur.

Although generally the ratio of the sulfurchloride to the substituted p-phenylenediamine used in the reaction will be 0.5 to 2.0 moles of the sulfur chloride to 1.0 mole of the substituted p-phenylenediamine, a larger amount of the sulfur chloride may be used to produce a higher molecular weight product. Either sulfur monochloride or sulfur dichloride, or a mixture of the two, may be used.

A tread stock masterbatch was obtained by compounding a rubbery copolymer of butadiene and styrene, according to the following formula:

Compounding Formula Parts by weight Blank Test Control Masterbatch 159. 4 159. 4 159. 4 ulfide of Example 1 .l 2 SN ,Ndl-scc. butyl-p-phenylene-diamine 2 Total 159. 4 161. 4 161. 4 Physical properties:

Normal:

300% modulus 925 975 875 Tensile strength 3, 525 3, 800 3, 475 gercent elongation 605 615 620 e g 300% modulus 2,125 l, 975 1,925 Tensile strength. 2, 675 3, 100 3, 023 Percent elongation 350 410 405 Ozone effects (4 hrs. 60 pplun 95 F.):

Static:

Size Mod. sev. None None Frequency Mod-num. None None Dynamic:

Size Slight None None Frequency Numerous None None The product of the example was subjected to toxicity tests, for comparison with N,N-di-sec.-butyl-p-phenylenediamine, particularly with regard to sensitization. A 5 percent solution of each in cold cream was used in the tests. Fifteen subjects were tested in each instance except where there was interference by an imitative effect.

The severity of the reaction is indicated by the numberof plusses, and the table shows the severity with respect to each subject tested.

Sensitivity Efiect v Num- ber Degree Rating subjects Sulfide of Example 1 Moderately sensitizing.

H HOOl-ONJWUIN Extremely sensitizing. ylenedianu'ne.

Hevea rubber tread stock having the following composition:

Rubber 100 HAF black 50 Zinc oxide 3 Stearic acid 2.6

Softener 3 Retarder 1.0 Accelerator 0.5 Sulfur 2.6 Antiozone agent 1.8

cracked. After two months, the two stocks were equally 7 well protected.

The products of Examples 2 to 4, inclusive, were compared to N,N-di( l-methylheptyl) -p-phenylenediamine,

the compound from which they were derived, in an The stockswere cured 40 minutes at 280 F.

After exposure of test strips for 7 hours in the weathering machine to an ozone concentration of 60 pphm. at F., the rubbers containing the antiozonants of Examples 2 to 4 were equal to or slightly better than the rubber containing the parent compound, N,N-di(1- methylheptyl)-p-phenylenediamine. With such tread stock, the advantage of a stock containing such an antiozonant over a blank stock (no antiozonant) is evident in the dynamic test results. Hence these results demonstrate the antiozonant value of the products of Examples 2 to 4.

The products of Examples 5 to 7, inclusive, were compared to di-sec-butyi-p-phenylenediarnine, the compound from which they were derived, in the same Hevea tread stock as was used in testing the antiozonants of Examples 2 to 4. After exposure of test strips for 7 hours in the weathering machine to an ozone concentration of 60 pphm. at 95 F, therubbers containing the antiozonants of Examples 5 to 7 were equal to the rubber containing the parent compound. Since the parent compound is a recognized antiozonant, the value of the products of Examples 5 to 7 as antiozonants is clearly demonstrated.

The examples and test data are merely illustrative. This application is a continuation-in-part of my application Serial No. 562,576, filed January 31; 1956, now abandoned. The invention is defined in the claim which follows.

substantially simultaneous neutralization of the hydrogen chloride formed.

References Cited in the file of this patent UNITED STATES PATENTS 2,187,155 Ingram Jan. 16, 1940 2,747,005 Zerbe et al May 22, 1956 2,766,236 Harman Oct. 9, 1956 7 2,905,655 Albert Sept. 22, 1959 OTHER REFERENCES Ellis: Chemistry of Petroleum Derivatives, page 764 (1934).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,100,765 August 13, 1963 Harry E. Albert It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, line 48,

for "outline" read outlined column 5, in the first table, first column, line 2 thereof, for "ulfide" read Sulfide same table, first column, line 3 thereof, for "SN,N read N,N

Signed and sealed this 24th day of August 1965,

(SEAL) A tlcsl:

ERNEST W. SWIDER EDWARD J. BRENNER A ttcsting Officer Commissioner of Patents 

